Solid state electrolytes

ABSTRACT

A solid state electrolyte comprising an ionically conducting product of a fused ternary mixture of lead fluoride, an alkali salt of sodium, potassium, rubidium or cesium in a range of 0.1 to 15.0 mole percent and a fluoride, nitrate or sulfate of magnesium, calcium, strontium or barium in a range of between 1 and 40 mole percent.

FIELD OF THE INVENTION

The invention relates to a solid state electrolyte based on a fused ternary mixture containing lead fluoride.

BACKGROUND OF THE INVENTION

Ionic conductivity is usually associated with the flow of ions through an aqueous solution of metallic salts. In the vast majority of practical uses of ionic conductors, i.e., as electrolytes for dry cell batteries, the aqueous solution is immobilized in a paste or gelled matrix to overcome the difficulties associated with handling and packaging a liquid. However, even after immobilization, the system is still subject to possible leakage, has a limited shelf life due to drying out or crystallization of the salts and is suitable for use only within a limited temperature range corresponding to the liquid range of the electrolyte. In addition, the necessity of including a large volume of immobilizing material has hindered the aims of miniaturization.

In attempting to overcome the shortcomings of liquid systems, investigators have surveyed a large number of solid compounds hoping to find compounds which are solid at room temperature and have specific conductances approaching those exhibited by the commonly used liquid system. Most solids have specific conductances at room temperature (20° C.) in the range of 10⁻⁶ to 10⁻¹⁵ ohm⁻¹ cm.⁻¹ as compared to aqueous solutions of salts which nominally have a specific conductance of 0.5 to 0.8 ohm⁻¹ cm.⁻¹.

In addition to the shortcomings of liquid systems, improved microelectronic circuit designs have generally decreased the current requirements for electronic devices. This in turn has enhanced the applicability of solid electrolyte power sources which usually can only deliver currents in the microampere range. These solid electrolyte systems have the inherent advantages of being free of electrolyte leakage and internal gassing problems due to the absence of a liquid phase and corrosion phenomena. In addition, they also have a much longer shelf life than the conventional liquid power sources.

Solid electrolytes must be essentially electronic insulators so as not to internally short the cell while at the same time they must allow ionic movement in the crystal lattice for the cell to operate. It has been discovered that certain metallic salts which are solids at room temperatures have specific conductances sufficiently high to permit their use in practical battery applications. For example, U.S. Pat. No. 3,723,185 discloses solid state electrolytes of compounds conforming to the general formula AgI-MCN-AgCN or modifications thereof wherein M is potassium, rubidium, cesium of mixtures thereof.

Filed concurrently herewith by applicant and incorporated herein by reference in U.S. application Ser. No. 973,554 titled Solid State Electrolyte disclosing a relatively highly conducting solid state electrolyte made from a binary mixture of lead fluoride and a 0.1 to 15.0 mole percent of a selected alkali salt of sodium, potassium, rubidium and cesium.

It is an object of the present invention to provide a novel ionically conductive product that is solid at room temperature and has a high conductance to permit its use as a solid state electrolyte for battery applications.

Another object of the present invention is to provide a novel solid state electrolyte for battery applications that is essentially an electronic insulator so as not to internally short the cell in which it is to be used while at the same time it will allow ionic movement in the crystal lattice.

Another object of the present invention is to provide a novel solid state electrolyte of a fused ternary mixture containing lead fluoride as its major component and having a highly stable ionic conductivity at room temperature thus making it admirably suitable for battery applications.

It is another object of the present invention to provide a highly conducting solid electrolyte based on lead fluoride.

The foregoing and additional objects will become more fully apparent from the following description.

SUMMARY OF THE INVENTION

The invention relates to a solid state electrolyte comprising an ionically conductive product of a fused ternary mixture of lead fluoride (PbF₂), an alkali salt selected from the group of sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs) salts in a range of between about 1.0 and about 15.0 mole percent and a fluoride, nitrate or sulfate of magnesium, calcium, strontium or barium in a range between about 1 and about 40 mole percent. Preferably the range of the former should be between about 1 and about 5 and the range of the latter should be between about 3 and about 10 mole percent based on the electrolyte.

Preferably the ionic conductivity of the solid state electrolyte of this invention should be at least 10⁻⁵ ohm⁻¹ centimeter⁻¹.

Suitable alkali salts would be potassium fluoride, rubidium fluoride, cesium fluoride, potassium carbonate, potassium sulfate and potassium nitrate. Suitable fluorides would be strontium fluoride, calcium fluoride, barium fluoride and magnesium fluoride. Suitable nitrates would be calcium nitrate and strontium nitrate. Suitable sulfates would be calcium sulfate, barium sulfate and strontium sulfate.

While both alpha-PbF₂ and beta-PbF₂ are anionic conductors, the beta-PbF₂ is more conductive but, nonetheless, neither is of the low resistivity that would be highly desirable in a solid electrolyte application. Beta-PbF₂ has a specific resistivity of about 5×10⁶ ohm-cm, while that of alpha-PbF₂ is about 5×10⁷ ohm-cm. If ordinary lead fluoride is heated for a short time above about 350° C. and then cooled, it is entirely converted to the beta form with a characteristic X-ray pattern. However, it has been observed that when this material is compressed to make a pellet for a conductivity measurement, it transforms partially to the alpha form. Although the resistivity of beta-PbF₂ is at levels marginally useful as a solid electrolyte in battery applications, the instability and reversion to the alpha form manifests itself in an increasing resistivity with increase of pressure such as would be employed in the fabrication of a solid electrolyte battery and with increase of temperature and age such as might be experienced during storage of a battery.

It has been discovered that, with the addition of the above-referred to alkali salts in a range between about 0.1 and about 15.0 mole percent and the above-referred to fluorides, nitrates and sulfates in the range of 1 to 40 mole percent to the lead fluoride, the product of the fused ternary mixture produced will have a high ionic conductivity thereby making it suitable for use in battery applications as a solid state electrolyte. It was also unexpectedly found that the addition of the above-referred to materials to lead fluoride had a very beneficial stabilizing effect on the ionic conductivity of the lead fluoride. As used herein, the term "stability" when referring to ionic conductivity shall mean the constancy of ionic conductivity with pressure, temperature and age. As stated above, stability of the ionic conductivity of a solid anionically conductive material is necessary if it is to be used as a solid state electrolyte in battery applications.

EXAMPLE I

Several lead fluoride-containing solid state electrolytes were prepared in the following manner. Lead fluoride along with the specific additions shown in Table I were separately vacuum dried at 140° C. for about an hour. The materials were then intimately mixed, placed in a platinum boat contained in a quartz vessel flushed with argon, and slowly heated up to as high as 850° C. to melt the materials. In the case of easily decomposable or volatile salts, slow heating was used to the minimum temperature necessary to melt the mixture. The melt was thereafter held at this temperature for 15 to 20 minutes to insure a homogeneous mixture. The solidified material was easily removed from the boat on cooling, transferred to a dry box and crushed in an agate mortar. The materials were thereafter formed into pellets measuring 1 sq. cm. cross section by 0.5 to 1.0 cm thick using a Carver Laboratory press operating at 45,000 psi. The resistivity of each pellet was measured and the results obtained are shown in Table I. As evident from the data shown in Table I, the resistivity of lead fluoride which is from 10⁶ to 10⁷ ohm-cm decreased with the addition of the materials shown to values as low as 642 ohm-cm.

                  TABLE I                                                          ______________________________________                                         Mixture          Specific Resistivity                                          Composition (Molar)                                                                             (ohm-cm) at Room Temp.                                        ______________________________________                                         86PbF.sub.2 -10CaF.sub.2 -4KF                                                                   1578                                                          81PbF.sub.2 -15CaF.sub.2 -4KF                                                                   2750                                                          76PbF.sub.2 -20CaF.sub.2 -4KF                                                                   2200                                                          71PbF.sub.2 -25CaF.sub.2 -4KF                                                                   2500                                                          66PbF.sub.2 -35CaF.sub.2 -4KF                                                                   1730                                                          61PbF.sub.2 -35CaF.sub.2 -4KF                                                                   1800                                                          79PbF.sub.2 -6KF-15SrF.sub.2                                                                    10778                                                         77PbF.sub.2 -8KF-15SrF.sub.2                                                                    1736                                                          75PbF.sub.2 -10KF-15SrF.sub.2                                                                   3000                                                          86PbF.sub.2 -10BaF.sub.2 -4KF                                                                   1100                                                          81PbF.sub.2 -15BaF.sub.2 -4KF                                                                   2800                                                          76PbF.sub.2 -20BaF.sub.2 -4KF                                                                   4400                                                          71PbF.sub.2 -25BaF.sub.2 -4KF                                                                   14000                                                         66PbF.sub.2 -30BaF.sub.2 -4KF                                                                   113000                                                        61PbF.sub.2 -35BaF.sub.2 -4KF                                                                   132000                                                        56PbF.sub.2 -40BaF.sub.2 -4KF                                                                   483000                                                        86PbF.sub.2 -10SrF.sub.2 -4RbF                                                                  2660                                                          86PbF.sub.2 -10SrF.sub.2 -4KF                                                                   1477                                                          81PbF.sub.2 -15SrF.sub.2 -4KF                                                                   2413                                                          76PbF.sub.2 -20SrF.sub.2 -4KF                                                                   3544                                                          71PbF.sub.2 -25SrF.sub.2 -4KF                                                                   9310                                                          66PbF.sub.2 -30SrF.sub.2 -4KF                                                                   26000                                                         61PbF.sub.2 -35SrF.sub.2 -4KF                                                                   70000                                                         56PbF.sub.2 -40SrF.sub.2 -4KF                                                                   269000                                                        88PbF.sub.2 -8SrF.sub.2 -4LiF                                                                   380000                                                        88PbF.sub.2 8SrF.sub.2 -4NaF                                                                    20000                                                         88PbF.sub.2 8SrF.sub.2 -4RbF                                                                    5700                                                          88PbF.sub.2 -8SrF.sub.2 -4CsF                                                                   63000                                                         88PbF.sub.2 8SrF.sub.2 -4RbCl                                                                   4100                                                          76PbF.sub.2 -20CaF.sub.2 -4RbF                                                                  5200                                                          76PbF.sub.2 -20BaF.sub.2 -4RbF                                                                  6500                                                          81PbF.sub.2 -15SrF.sub.2 -4KBr                                                                  5200                                                          81PbF.sub.2 -15SrF.sub.2 -4K.sub.2 CO.sub.3                                                     7100                                                          81PbF.sub.2 -15SrF.sub.2 -4K.sub.2 SO.sub.4                                                     8500                                                          76PbF.sub.2 -20SrF.sub.2 -4KBr                                                                  7500                                                          76PbF.sub.2 -20SrF.sub.2 -4K.sub.2 CO.sub.3                                                     9800                                                          76PbF.sub.2 -20SrF.sub.2 -4K.sub.2 SO.sub.4                                                     18400                                                         96PbF.sub.2 -2CaF.sub.2 -2KF                                                                    1326                                                          94PbF.sub.2 -3CaF.sub.2 -3KF                                                                    827                                                           95PbF.sub.2 -2CaF.sub.2 -3KF                                                                    766                                                           94PbF.sub.2 -2CaF.sub.2 -4KF                                                                    642                                                           95PbF.sub.2 -3CaF.sub.2 -2KF                                                                    1134                                                          94PbF.sub.2 -1CaF.sub.2 -5RbCl                                                                  3450                                                          96PbF.sub.2 -2MgF.sub.2 -2KF                                                                    3630                                                          94PbF.sub.2 -1MgF.sub.2 -5KF                                                                    2430                                                          94PbF.sub.2 -2MgF.sub.2 -4KF                                                                    1108                                                          96PbF.sub.2 -2MgF.sub.2 -2K.sub.2 CO.sub.3                                                      4400                                                          94PbF.sub.2 -1MgF.sub.2 -5K.sub.2 CO.sub.3                                                      1047                                                          94PbF.sub.2 -1MgF.sub.2 -4K.sub.2 CO.sub.3                                                      1161                                                          88PbF.sub.2 -8MgF.sub.2 -4KF                                                                    26400                                                         86PbF.sub.2 -10MgF.sub.2 -4KF                                                                   21900                                                         76PbF.sub.2 -20MgF.sub.2 -4KF                                                                   40200                                                         90PbF.sub.2 -5SrF.sub.2 -5KF                                                                    848                                                           88PbF.sub.2 -8SrF.sub.2 -2K.sub.2 CO.sub.3                                                      1970                                                          90PbF.sub.2 -8SrF.sub.2 -2K.sub.2 CO.sub.3                                                      1202                                                          86PbF.sub.2 -10CaF.sub.2 -2K.sub.2 CO.sub.3                                                     1815                                                          86PbF.sub.2 -10SrF.sub.2 -2K.sub.2 CO.sub.3                                                     1405                                                          96PbF.sub.2 -2Sr(NO.sub.3).sub.2 -2KNO.sub.3                                                    1078                                                          86PbF.sub.2 10Sr(NO.sub.3).sub.2 -4KNO.sub.3                                                    8290                                                          86PbF.sub.2 -10SrF.sub.2 4KNO.sub.3                                                             1450                                                          *88PbF.sub.2 -8SrF.sub.2 -4KF                                                                   857                                                           90PbF.sub.2 -6SrF.sub.2 -4KF                                                                    1034                                                          94.5PbF.sub.2 -0.5CaSO.sub.4 -5.0KF                                                             1136                                                          94.5PbF.sub.2 -0.5CaSO.sub.4 -5.0K.sub.2 CO.sub.3                                               1164                                                          88PbF.sub.2 -8SrF.sub.2 -4K.sub.2 SO.sub.4                                                      5700                                                          88PbF.sub.2 -8SrF.sub.2 -4KNO.sub.3                                                             1900                                                          88PbF.sub.2 -8SrF.sub.2 -4KCl                                                                   20000                                                         88PbF.sub.2 -8SrF.sub.2 -4KBr                                                                   2500                                                          88PbF.sub.2 -8SrF.sub.2 -4K.sub.2 CO.sub.3                                                      1700                                                          88PbF.sub.2 -8BaF.sub.2 -4KF                                                                    1050                                                          88PbF.sub.2 -8BaF.sub.2 -4K.sub.2 SO.sub.4                                                      5900                                                          88PbF.sub.2 -4CaF.sub.2 -4SrF.sub.2 -4KF                                                        4000                                                          88PbF.sub.2 -4CaF.sub.2 -4SrF.sub.2 -4K.sub.2 SO.sub.4                                          15600                                                         ______________________________________                                          *The ionically conducting product formed from this ternary mixture was         analyzed and found to contain the following: 78.63 wt./percent lead, 3.07      wt./percent strontium, 15.97 wt./percent fluorine and 0.60 wt./percent         potassium.                                                               

EXAMPLE II

A lead disc anode, a solid electrolyte made from the molar mixture of 88PbF₂ -8SrF₂ -4KF and a cathode consisting of a 1:1 molar mixture of MnF₃ and PbO₂ which was further diluted with about 30 wt. % of the electrolyte was compressed together in a cavity of 1-cm² cross section at about 12,000 psi. The open circuit voltage of the cell so produced was 1.60 volts and when discharged across a 500-K-ohm resistor, the initial closed circuit voltage was 1.56 volts.

EXAMPLE III

A cell was prepared as in Example II with the exception that the cathode was a 1:1 molar mixture of CoF₃ and PbO₂. The open circuit voltage of the cell so produced was 1.9 volts and fell to 1.88 volts initially when a 100-K-ohm resistor was connected across the cell.

EXAMPLE IV

To further test the solid state electrolyte of this invention in a cell, a sheet-lead anode, a solid electrolyte made from the molar mixture 88PbF₂ -8SrF₂ -4KF and a lead dioxide (PbO₂) cathode were assembled together to form a cell. The open circuit voltage of the cell so produced was 1.192 volts and when discharged across a 500-K-Ohm resistor, the initial closed circuit voltage was 1.170 volts. Under this load condition, the initial current density was calculated to be 2.3 μA/cm². Thus the solid state electrolyte of this invention is admirably suited for battery applications.

EXAMPLE V

A cell was constructed as described in Example IV with the exception that the cathode was electrolytic manganese dioxide mixed with the electrolyte made from the molar mixture 88PbF₂ -8 SrF₂ -4KF. The open circuit voltage of the cell so produced was 1.088 volts and when discharged across a 500-K-ohm resistor, the initial closed circuit voltage was 1.082 volts.

EXAMPLE VI

Several additional cells were prepared using an anode of lead, a solid electrolyte made from the molar mixture 88PbF₂ -8SrF₂ -4FK and a cathode as shown in Table II. The open circuit voltage of each cell produced was measured and is shown in Table II. From the data shown in Table II it is evident that the solid state electrolytes of this invention can be admirably suited for battery applications.

                  TABLE II                                                         ______________________________________                                         Cathode    O.C.V.   Cathode         O.C.V.                                     Material   (Volts)  Material        (Volts)                                    ______________________________________                                         HgF.sub.2 + graphite                                                                      1.20     CF.sub.x        0.50                                       AgF.sub.2 + graphite                                                                      1.90     EMD(MnO.sub.2)/HgO                                                                             1.05                                       BiF.sub.3 + graphite                                                                      0.86     CoF.sub.3.MnO.sub.2                                                                            1.23                                       CoF.sub.3 + graphite                                                                      1.35     BrF.sub.3.PbO.sub.2                                                                            1.11                                       MnF.sub.3 + graphite                                                                      0.26     MnF.sub.3.PbO.sub.2                                                                            1.71                                       PbO.sub.2  1.04     CoF.sub.3.PbO.sub.2                                                                            1.90                                       YF.sub.3 + graphite                                                                       0.95     TaF.sub.5.PbO.sub.2                                                                            1.80                                       AuF.sub.3 + graphite                                                                      1.24     V.sub.2 O.sub.5 0.85                                       FeF.sub.2 + graphite                                                                      1.04     FeS.sub.2       0.53                                       FeF.sub.3 + graphite                                                                      0.66     WO.sub.3        0.185                                      EMD(MnO.sub.2)                                                                            1.09     CoF.sub.3.HlO.sub.3                                                                            1.625                                      MnF.sub.3 /MnO.sub.2                                                                      1.30     TaF.sub.5 + graphite                                                                           0.69                                       CuF.sub.2 + graphite                                                                      0.80     TaF.sub.5.MnF.sub.3 + graphite                                                                 1.52                                       ______________________________________                                    

As evident from the examples above the solid state electrolyte of this invention can be used with various cell systems employing an anode such as lead or any metal more noble than lead and fluoride-containing solid cathodes. 

What is claimed is: .[.
 1. A solid state cell electrolyte comprising an ionically conducting produce of a fused ternary mixture of lead fluoride, an alkali salt selected from the group consisting of sodium, potassium rubidium and cesium salts in a range of between about 1.0 and about 15.0 mole percent and a fluoride, nitrate or sulfate of magnesium, calcium, strontium or barium in a range between about 1 and about 40 mole percent..]. .[.2. The solid state cell electrolyte of claim 1 wherein the alkali salt is selected from the group consisting of potassium fluoride, rubidium fluoride, cesium fluoride, potassium carbonate, potassium sulfate and potassium nitrate..]. .[.3. The solid state cell electrolyte of claim 1 wherein the fluoride is selected from the group consisting of strontium fluoride, calcium fluoride, barium fluoride and magnesium fluoride..]. .[.4. The solid state cell electrolyte of claim 1 wherein the nitrate is selected from the group consisting of calcium nitrate and strontium nitrate..]. .[.5. The solid state cell electrolyte of claim 1 wherein the sulfate is selected from the group consisting of calcium sulfate, barium sulfate and strontium sulfate..]. .[.6. The solid state electrolyte of claim 1 wherein the ionically conducting produce is formed from the fused ternary mixture 88PbF₂ -8SrF₂ -4KF..]. .[.7. The solid state electrolyte of claim 1 wherein the ionically conducting product is formed from the fused ternary mixture 94PbF₂ -3CaF₂ -3KF..]. .[.8. The solid state electrolyte of claim 1 wherein the ionically conducting product is formed from the fused ternary mixture 95PbF₂ -2CaF₂ -3KF..]. .[.9. The solid state electrolyte of claim 1 wherein the ionically conducting product is formed from the fused ternary mixture 94PbF₂ -2CaF₂ -4KF..]. .[.10. The solid state electrolyte of claim 1 wherein the ionically conducting product is formed from the fused ternary mixture 86PbF₂ -10SrF₂ -4KF..]. .[.11. The solid state electrolyte of claim 1 wherein the ionically conducting product is formed from the fused ternary mixture 86PbF₂ -10BaF₂ -4KF..]. .[.12. The solid state electrolyte of claim 1 wherein the ionically conducting product is formed from the fused ternary mixture 94PbF₂ -2MgF₂ -4KF..]. .Iadd.13. A solid state cell electrolyte comprising an ionically conducting product of a fused ternary mixture of lead fluoride, an alkali salt selected from the group consisting of sodium salts, cesium salts and nonfluoride-containing salts of potassium and rubidium in a range of between about 1.0 and about 15.0 mole percent and a fluoride, nitrate or sulfate of magnesium, calcium, strontium or barium in a range of between about 1 and about 40 mole percent. .Iaddend. .Iadd.14. The solid state cell electrolyte of claim 13 wherein the alkali salt is selected from the group consisting of cesium fluoride, potassium carbonate, potassium sulfate and potassium nitrate. .Iaddend. .Iadd.15. The solid state cell electrolyte of claim 13 wherein the fluoride is selected from the group consisting of strontium fluoride, calcium fluoride, barium fluoride and magnesium fluoride. .Iaddend. .Iadd.16. The solid state cell electrolyte of claim 13 wherein the nitrate is selected from the group consisting of calcium nitrate and strontium nitrate. .Iaddend. .Iadd.17. The solid state cell electrolyte of claim 13 wherein the sulfate is selected from the group consisting of calcium sulfate, barium sulfate and strontium sulfate. .Iaddend. 